Gold and silver complexes with the ferrocenyl phosphine FcCH2PPh2

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc = (eta5-C5H5)Fe(eta5-C5H4)] of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M = Au, Ag) have been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2CH2Fc)3]X (M = Au, X = ClO4; M = Ag, X = OTf) have been obtained from the corresponding gold and silver precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal structures of [AuR(PPh2CH2Fc)] (R = Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L = PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.     

Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(μ-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.     

Highly luminescent gold(I)-silver(I) and gold(I)-copper(I) chalcogenide clusters

The reactions of [AuClL] with Ag(2)O, where L represents the heterofunctional ligands PPh(2)py and PPh(2)CH(2)CH(2)py, give the trigoldoxonium complexes [O(AuL)(3)]BF(4). Treatment of these compounds with thio- or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)(3)]BF(4) (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)(4)]PF(6) to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh(2)py)(3)]BF(4) with silver or copper salts give [E(AuPPh(2)py)(3)M](2+) (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au(3)Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh(2)py)(3)](+) units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh(2)CH(2)CH(2)py)(3)]BF(4) with silver and copper salts give complexes with [E(AuPPh(2)CH(2)CH(2)py)(3)M](2+) stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of AuM interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.     

New group 11 complexes with metal-selenium bonds of methyldiphenylphosphane selenide: a solid state, solution and theoretical investigation

Reactions between methyldiphenylphosphane selenide, SePPh(2)Me, and different group 11 metal starting materials {CuCl, [CuNO(3)(PPh(3))(2)], AgOTf, [AgOTf(PPh(3))] (OTf = OSO(2)CF(3)), [AuCl(tht)], [Au(C(6)F(5))(tht)] and [Au(C(6)F(5))(3)(tht)] (tht = tetrahydrothiophene)} were performed in order to obtain several new species with metal-selenium bonds. The new complexes [CuCl(SePPh(2)Me)] (1), [AgOTf(SePPh(2)Me)] (2), [AuCl(SePPh(2)Me)] (5), [Au(C(6)F(5))(SePPh(2)Me)] (6) and [Au(C(6)F(5))(3)(SePPh(2)Me)] (7) were isolated and structurally characterized in solution by multinuclear NMR spectroscopy ((1)H, (31)P, (77)Se and (19)F where appropriate). Solid products were isolated also from the reactions between SePPh(2)Me and [CuNO(3)(PPh(3))(2)] or [AgOTf(PPh(3))], respectively. NMR experiments, including low temperature (1)H and (31)P NMR, revealed for them a dynamic behaviour in solution, involving the transfer of selenium from PPh(2)Me to PPh(3). In case of the isolated silver(i) containing solid an equilibrium between, respectively, monomeric [AgOTf(PPh(3))(SePPh(2)Me)] (3) and [AgOTf(PPh(2)Me)(SePPh(3))] (4), and dimeric [Ag(PPh(3))(μ-SePPh(2)Me)](2)(OTf)(2) (3a) and [Ag(PPh(2)Me)(μ-SePPh(3))](2)(OTf)(2) (4a) species was observed in solution. In case of the isolated copper(i) containing solid the NMR studies brought no clear evidence for a similar behaviour, but it can not be excluded in a first stage of the reaction. However the transfer of selenium between the two triorganophosphanes takes place also in this case, but the NMR spectra suggest that the final reaction mixture contains the free triorganophospane selenides SePPh(2)Me and SePPh(3) as well as the complex species [CuNO(3)(PPh(3))(2)], [CuNO(3)(PPh(2)Me)(2)] and [CuNO(3)(PPh(3))(PPh(2)Me)] in equilibrium. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) 6 and gold(III) 7 complexes. In case of compound 6 weak aurophilic gold(I)···gold(I) contacts were also observed in the crystal. DFT calculations were performed in order to understand the solution behaviour of the silver(I) and copper(I) species containing both P(III) and P(V) ligands, to verify the stability of possible dimeric species and to account for the aurophilic interactions found for 6. In addition, the nature of the electronic transitions involved in the absorption/emission processes observed for 6 and 7 in the solid state were also investigated by means of TD-DFT calculations.     

Behavior of neutral phosphido derivatives of platinum and palladium toward silver centers

The reaction of the neutral binuclear complexes [(R(F))(2)Pt(μ-PPh(2))(2)M(phen)] (phen = 1,10-phenanthroline, R(F) = C(6)F(5); M = Pt, 1; M = Pd, 2) with AgClO(4) or [Ag(OClO(3))(PPh(3))] affords the trinuclear complexes [AgPt(2)(μ-PPh(2))(2)(R(F))(2)(phen)(OClO(3))] (7a) or [AgPtM(μ-PPh(2))(2)(R(F))(2)(phen)(PPh(3))][ClO(4)] (M = Pt, 8; M = Pd, 9), which display an "open-book" type structure and two (7a) or one (8, 9) Pt-Ag bonds. The neutral diphosphine complexes [(R(F))(2)Pt(μ-PPh(2))(2)M(P-P)] (P-P = 1,2-bis(diphenylphosphino)methane, dppm, M = Pt, 3; M = Pd, 4; P-P = 1,2-bis(diphenylphosphino)ethane, dppe, M = Pt, 5; M = Pd, 6) react with AgClO(4) or [Ag(OClO(3))(PPh(3))], and the nature of the resulting complexes is dependent on both M and the diphosphine. The dppm Pt-Pt complex 3 reacts with [Ag(OClO(3))(PPh(3))], affording a silver adduct 10 in which the Ag atom interacts with the Pt atoms, while the dppm Pt-Pd complex 4 reacts with [Ag(OClO(3))(PPh(3))], forming a 1:1 mixture of [AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(dppm)] (11), in which the silver atom is connected to the Pt-Pd moiety through Pd-(μ-PPh(2))-Ag and Ag-P(k(1)-dppm) interactions, and [AgPdPt(μ-PPh(2))(2)(R(F))(2)(OClO(3))(PPh(3))(2)][ClO(4)] (12). The reaction of complex 4 with AgClO(4) gives the trinuclear derivative 11 as the only product. Complex 11 shows a dynamic process in solution in which the silver atom interacts alternatively with both Pd-μPPh(2) bonds. When P-P is dppe, both complexes 5 and 6 react with AgClO(4) or [Ag(OClO(3))(PPh(3))], forming the saturated complexes [(PPh(2)C(6)F(5))(R(F))Pt(μ-PPh(2))(μ-OH)M(dppe)][ClO(4)] (M = Pt, 13; Pd, 14), which are the result of an oxidation followed by a PPh(2)/C(6)F(5) reductive coupling. Finally, the oxidation of trinuclear derivatives [(R(F))(2)Pt(II)(μ-PPh(2))(2)Pt(II)(μ-PPh(2))(2)Pt(II)L(2)] (L(2) = phen, 15; L = PPh(3), 16) by AgClO(4) results in the formation of the unsaturated 46 VEC complexes [(R(F))(2)Pt(III)(μ-PPh(2))(2)Pt(III)(μ-PPh(2))(2)Pt(II)L(2)][ClO(4)](2) (17 and 18, respectively) which display Pt(III)-Pt(III) bonds.     

Dithiocarboxylate complexes of ruthenium(II) and osmium(II)

The ruthenium(II) complexes [Ru(R)(κ(2)-S(2)C·IPr)(CO)(PPh(3))(2)](+) (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C≡CPh)=CHPh) are formed on reaction of IPr·CS(2) with [Ru(R)Cl(CO)(BTD)(PPh(3))(2)] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C≡CPh)=CHPh)Cl(CO)(PPh(3))(2)] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2)](+) and [Ru(C(C≡CPh)=CHPh)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2)](+) are formed in the same manner when ICy·CS(2) is employed. The ligand IMes·CS(2) reacts with [Ru(R)Cl(CO)(BTD)(PPh(3))(2)] to form the compounds [Ru(R)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2)](+) (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C≡CPh)=CHPh). Two osmium analogues, [Os(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2)](+) and [Os(C(C≡CPh)=CHPh)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2)](+) were also prepared. When the more bulky diisopropylphenyl derivative IDip·CS(2) is used, an unusual product, [Ru(κ(2)-SC(H)S(CH=CHC(6)H(4)Me-4)·IDip)Cl(CO)(PPh(3))(2)](+), with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH=CHC(6)H(4)Me-4)Cl(BTD)(CO)(PPh(3))(2)] also reacts with IMes·CS(2) and NH(4)PF(6) to yield the analogous product [Ru{κ(2)-SC(H)S(CH=CHC(6)H(4)Me-4)·IMes}Cl(CO)(PPh(3))(2)](+)via the intermediate [Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IMes)(CO)(PPh(3))(2)](+). Structural studies are reported for [Ru(CH=CHC(6)H(4)Me-4)(κ(2)-S(2)C·IPr)(CO)(PPh(3))(2)]PF(6) and [Ru(C(C≡CPh)=CHPh)(κ(2)-S(2)C·ICy)(CO)(PPh(3))(2)]PF(6).     

Heterolytic cleavage of dihydrogen promoted by sulfido-bridged tungsten-ruthenium dinuclear complexes

A series of sulfido-bridged tungsten-ruthenium dinuclear complexes Cp*W(mu-S)(3)RuX(PPh(3))(2) (4a; X = Cl, 4b; X = H), Cp*W(O)(mu-S)(2)RuX(PPh(3))(2) (5a; X = Cl, 5b; X = H), and Cp*W(NPh)(mu-S)(2)RuX(PPh(3))(2) (6a; X = Cl, 6b; X = H) have been synthesized by the reactions of (PPh(4))[Cp*W(S)(3)] (1), (PPh(4))[Cp*W(O)(S)(2)] (2), and (PPh(4))[Cp*W(NPh)(S)(2)] (3), with RuClX(PPh(3))(3) (X = Cl, H). The heterolytic cleavage of H(2) was found to proceed at room temperature upon treating 5a and 6a with NaBAr(F)(4) (Ar(F) = 3, 5-C(6)H(3)(CF(3))(2)) under atmospheric pressure of H(2), which gave rise to [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (7a) and [Cp*W(NHPh)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (8), respectively. When Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b) was treated with a Br?nstead acid, [H(OEt(2))(2)](BAr(F)(4)) or HOTf, protonation occurred exclusively at the terminal oxide to give [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](X) (7a; X = BAr(F)(4), 7b; X = OTf), while the hydride remained intact. The analogous reaction of Cp+W(mu-S)(3)Ru(PPh(3))(2)H (4b) led to immediate evolution of H(2). Selective deprotonation of the hydroxyl group of 7a or 7b was induced by NEt(3) and 4b, generating Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b). Evolution of H(2) was also observed for the reactions of 7a or 7b with CH(3)CN to give [Cp*W(O)(mu-S)(2)Ru(CH(3)CN)(PPh(3))(2)](X) (11a; X = BAr(F)(4), 11b; X = OTf). We examined the H/D exchange reactions of 4b, 5b, and 7a with D(2) and CH(3)OD, and found that facile H/D scrambling over the W-OH and Ru-H sites occurred for 7a. Based on these experimental results, the mechanism of the heterolytic H(2) activation and the reverse H(2) evolution reactions are discussed.     

Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands

The reaction of the unsymmetrical ligands 1-diphenylphosphino-1'-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1'-(phenylselenyl)ferrocene, Fc(EPh)PPh2(E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}](M = Au, X = Cl, C6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO4, [Au(C6F5)3{Fc(EPh)PPh2}], [Au2(C6F5)6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2}2]PF6(E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au...Cl or Au...Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands.     

Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(mu-L)2(OH2)2](OTf)2

The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 (1), with crystallographic mirror symmetry, or dinuclear [Ag2(mu-L)2](OTf)2 (2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 (3); Ag, X = OTf 4). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf (5). The gold(I) derivative [Au2(C6F5)2(mu-L)] (6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1-4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.     

Luminescent copper(I) halide adducts of [Au(im(CH2py)2)2]PF6 exhibiting short Au(I)···Cu(I) separations and unusual semibridging NHC ligands

The picolyl-substituted NHC complex [Au(im(CH(2)py)(2))(2)]PF(6) (1) reacts with two equivalents of copper(I) halides, affording compounds [Au(im(CH(2)py)(2))(2)(CuX)(2)]PF(6) (X = Cl, 2; Br, 3; I, 4). Each complex contains a nearly linearly coordinated [Au(NHC)(2)](+) center where the two picolyl groups on each im(CH(2)py)(2) ligand chelate a single copper atom. The Cu(I) center resides in a distorted tetrahedral environment and is coordinated to two pyridyl groups, a halide ion, and a gold metalloligand. The Au(I)-Cu(I) separations measure 2.7030(5), 2.6688(9), and 2.6786(10) ? for 2-4, respectively. Additionally, each Cu(I) center is further coordinated by a semibridging NHC ligand with short Cu-C separations of ~2.3 ?. In solution, these complexes dissociate the Cu(I) ion. In the solid state, 2-4 are photoluminescent with respective emission maxima of 512, 502, and 507 nm. The reaction of [Au(im(CH(2)py)(2))(2)]PF(6) with four equivalents of CuBr afforded the coordination polymer {[AuCu(2)Br(2)(im(CH(2)py)(2))(2)]Br·3CH(3)CN}(n) (5). This polymeric complex contains [Au(NHC)(2)](+) units interconnected by Cu(2)Br(2) dimers. In 5, the Au-Cu separations are long at 4.23 and 4.79 ?, while the Cu-Cu distance is considerably shorter at 2.9248(14) ?. In the solid state, 5 is photoluminescent with a broad band appearing at 533 nm.     

Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I) centers

The monohapto neutral 2-(diphenylphosphino)aniline (PNH(2)) complexes [Au(C(6)F(5))(2)X(PNH(2))] (X = C(6)F(5) (1), Cl (2)) have been obtained from [Au(C(6)F(5))(3)(tht)] or [Au(C(6)F(5))(2)(micro-Cl)](2) and PNH(2), and the cationic [Au(C(6)F(5))(2)(PNH(2))]ClO(4) (3) has been similarly prepared from [Au(C(6)F(5))(2)(OEt(2))(2)]ClO(4) and PNH(2) or from 2 and AgClO(4). The neutral amido complex [Au(C(6)F(5))(2)(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac = acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO(3))(PPh(3))] or [Au(OClO(3))(PPh(3))] to give the dinuclear species [Au(C(6)F(5))(2)[PNH(MPPh(3))]]ClO(4) (M = Ag (5), Au (6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh(3))]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C(6)F(5))(2)[PN(AuPPh(3))(2)]]ClO(4) (7) is obtained. The crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)-Au(III) interaction.     

Selenolate gold complexes with aurophilic Au(I)-Au(I) and Au(I)-Au(III) interactions

The gold(I) selenolate compound [Au(2)(SePh)(2)(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) has been prepared by reaction of [Au(2)Cl(2)(mu-dppf)] with PhSeSiMe(3) in a molar ratio 1:2. This complex reacts with gold(I) or gold(III) derivatives to give polynuclear gold(I)-gold(I) or gold(I)-gold(III) complexes of the type [Au(4)(mu-SePh)(2)(PPh(3))(2)(mu-dppf)](OTf)(2), [Au(3)(C(6)F(5))(3)(mu-SePh)(2)(mu-dppf)], or [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)], with bridging selenolate ligands. The reaction of [Au(2)(SePh)(2)(mu-dppf)] with 1 equiv of AgOTf leads to the formation of the insoluble Ag(SePh) and the compound [Au(2)(mu-SePh)(mu-dppf)]OTf. The complexes [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)] and [Au(2)(mu-SePh)(mu-dppf)]OTf (two different solvates) have been characterized by X-ray diffraction studies and show the presence of weak gold(I)-gold(III) interactions in the former and intra- and intermolecular gold(I)-gold(I) inter-actions in the later.     

Synthesis and Reaction of [MnRe（CO）6（μ—SH）（μ—SC（H）PPr^i3）（PPh3）]

The synthesis,the crystal structure and the reaction of the hetero-binuclear complex[MnRe(CO)6(μ-SH）（μ-SC(H)PPr^i3)(PPh3)] are reported.The results of single crystal X-ray structure analysis showed that the fragments Mn(CO)3 and Re(CO)3 were bridged by SH and SC(H)PPr^i3.The title complexes can react with Bu^nLi and RX forming complexes MnRe(CO)6(μ-SR）（μ-SC(H)PPr^i3)(PPh3)](R=Me,CH2CH=CH2,SnBu3^n).     

Formation of diphenylphosphanylbutadienyl complexes by insertion of two P-coordinated alkynylphosphanes into a PtbondC6F5 bond: detection of intermediate and reaction products

The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento complexes are unstable in solution evolving firstly, through an unexpected formal 4-1 R (Ph, Tol) migration, to the intermediate diphosphanylbutadienyl isomer derivatives [Pt(C(6)F(5))(S)mu-[C(C(6)F(5))doublebondC(PPh(2))C(PPh(2))doublebondC(R)(2)]M(C(6)F(5))(2)] (16, 18) (X-ray, R=Ph, M=Pt) and, finally, to 1-pentafluorophenyl-2,3-bis(diphenylphosphanyl)naphthalene mononuclear complexes (17, 19) by annulation of a phenyl or tolyl group.     

Synthesis and characterization of ethylbis(2-pyridylethyl)amineruthenium complexes and two different types of C-H bond cleavage at an ethylene arm

Ruthenium complexes bearing ethylbis(2-pyridylethyl)amine (ebpea), which has flexible -C(2)H(4)- arms between the amine and the pyridyl groups and coordinates to a metal center in facial and meridional modes, have been synthesized and characterized. Three trichloro complexes, fac-[Ru(III)Cl(3)(ebpea)] (fac-[1]), mer-[Ru(III)Cl(3)(ebpea)] (mer-[1]), and mer-[Ru(II)Cl(3){η(2)-N(C(2)H(5))(C(2)H(4)py)═CH-CH(2)py}] (mer-[2]), were synthesized using the Ru blue solution. Formation of mer-[2] proceeded via a C-H activation of the CH(2) group next to the amine nitrogen atom of the ethylene arm. Reduction reactions of fac- and mer-[1] afforded a triacetonitrile complex mer-[Ru(II)(CH(3)CN)(3)(ebpea)](PF(6))(2) (mer-[3](PF(6))(2)). Five nitrosyl complexes fac-[RuX(2)(NO)(ebpea)]PF(6) (X = Cl for fac-[4]PF(6); X = ONO(2) for fac-[5]PF(6)) and mer-[RuXY(NO)(ebpea)]PF(6) (X = Cl, Y = Cl for mer-[4]PF(6); X = Cl, Y = CH(3)O for mer-[6]PF(6); X = Cl, Y = OH for mer-[7]PF(6)) were synthesized and characterized by X-ray crystallography. A reaction of mer-[2] in H(2)O-C(2)H(5)OH at room temperature afforded mer-[1]. Oxidation of C(2)H(5)OH in H(2)O-C(2)H(5)OH and i-C(3)H(7)OH in H(2)O-i-C(3)H(7)OH to acetaldehyde and acetone by mer-[2] under stirring at room temperature occurred with formation of mer-[1]. Alternative C-H activation of the CH(2) group occurred next to the pyridyl group, and formation of a C-N bond between the CH moiety and the nitrosyl ligand afforded a nitroso complex [Ru(II)(N(3))(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([8]) in reactions of nitrosyl complexes with sodium azide in methanol, and reaction of [8] with hydrochloric acid afforded a corresponding chloronitroso complex [Ru(II)Cl(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([9]).     

Osmabenzenes from the reactions of a dicationic osmabenzyne complex

Treatment of the osmabenzyne Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)Cl(2)(PPh(3))(2) (1) with 2,2'-bipyridine (bipy) and thallium triflate (TlOTf) produces the thermally stable dicationic osmabenzyne [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) (2). The dicationic osmabenzyne 2 reacts with ROH (R = H, Me) to give osmabenzene complexes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf, in which the metallabenzene ring deviates significantly from planarity. In contrast, reaction of the dicationic complex 2 with NaBH(4) produces a cyclopentadienyl complex, presumably through the osmabenzene intermediate [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf. The higher thermal stability of [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf relative to [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf can be related to the stabilization effect of the OR groups on the metallacycle. A theoretical study shows that conversion of the dicationic osmabenzyne complex [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) to a carbene complex by reductive elimination is thermodynamically unfavorable. The theoretical study also suggests that the nonplanarity of the osmabenzenes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf is mainly due to electronic reasons.     

Metal Complexes of Mesitylphosphine: Synthesis, Structure, and Spectroscopy

A series of primary phosphine homoleptic complexes [ML(4)](n)()(+)X(n)() (1, M = Ni, n = 0; 2, M = Pd, n = 2, X = BF(4); 3, M = Cu, n = 1, X = PF(6); 4, M = Ag, n = 1, X = BF(4); L = PH(2)Mes, Mes = 2,4,6-Me(3)C(6)H(2)] was prepared from mesitylphosphine and Ni(COD)(2), [Pd(NCMe)(4)][BF(4)](2), [Cu(NCMe)(4)]PF(6), and AgBF(4), respectively. Reactions of 1-4 with MeC(CH(2)PPh(2))(3) (triphos) or [P(CH(2)CH(2)PPh(2))(3)] (tetraphos) afforded the derivatives [M(L')L](n)()(+)X(n)() (L' = triphos; 6, M = Ni, n = 0; 7, M = Cu, n = 1, X = PF(6); 8, M = Ag, n = 1, X = BF(4); L' = tetraphos; 9, M = Pd, n = 2, X = BF(4)). Addition of NOBF(4) to 1 yielded the nitrosyl compound [NiL(3)(NO)]BF(4), 5. The solution structure and dynamics of 1-9 were studied by (31)P NMR spectroscopy (including the first reported analyses of a 12-spin system for 1-2). Complexes 1, 3, 6, and 7.solvent were characterized crystallographically. The structural and spectroscopic studies suggest that the coordination properties of L are dominated by its relatively small cone angle and that the basicity of L is comparable to that of more commonly used tertiary phosphines.     

Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions

Addition of two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht = tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM'(PPh2CH2SPh)2](CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(C6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO3 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH2SPh)2]CF3SO3 (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh2CH2SPh)2-(CF3CO2)2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5) (CF3CO2)2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.     

Conversion of [Pt(SRf)2(PPh2 -n(C6F5)n+ 1)2]( n = 0 or 1, Rf=C6HF4-4) through carbon-fluorine bond activation to [Pt(SRf)2(1,2-C6F4(SRf)-(PPh2))] and chiral [Pt(SRf)2(1,2-C6F4(SRf)(PPh(C6F5)))

Treatment of trans-[PtCl(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)](n = 0 or 1) with Pb(SC(6)HF(4)-4)(2) yields a mixture of monometallic cis/trans [Pt(SC(6)HF(4)-4)(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)], thiolate-bridged bimetallic cis/trans [Pt(2)(mu-SC(6)HF(4)-4)(2)(SC(6)HF(4)-4)(2)(PPh(2 - n)(C(6)F(5))(n + 1))(2)] and [Pt(SC(6)HF(4)-4)(2)(1,2-C(6)F(4)(SC(6)HF(4)-4)(PPh(2 - n)(C(6)F(5))(n))].     

Mononuclear and dinuclear palladium and nickel complexes of phosphinimine-based tridentate ligands

The tridentate bis-phosphinimine ligands O(1,2-C(6)H(4)N=PPh(3))(2)1, HN(1,2-C(2)H(4)N=PR(3))(2) (R = Ph 2, iPr 3), MeN(1,2-C(2)H(4)N=PPh(3))(2)4 and HN(1,2-C(6)H(4)N=PPh(3))(2)5 were prepared. Employing these ligands, monometallic Pd and Ni complexes O(1,2-C(6)H(4)N=PPh(3))(2)PdCl(2)6, RN(1,2-CH(2)CH(2)N=PPh(3))(2)PdCl][Cl] (R = H 7, Me 8), [HN(1,2-CH(2)CH(2)N=PiPr(3))(2)PdCl][Cl] 9, [MeN(1,2-CH(2)CH(2)N=PPh(3))(2)PdCl][PF(6)] 10, [HN(1,2-CH(2)CH(2)N=PPh(3))(2)NiCl(2)] 11, [HN(1,2-CH(2)CH(2)N=PR(3))(2)NiCl][X] (X = Cl, R = iPr 12, X = PF(6), R = Ph 13, iPr 14), and [HN(1,2-C(6)H(4)N=PPh(3))(2)Ni(MeCN)(2)][BF(4)]Cl 15 were prepared and characterized. While the ether-bis-phosphinimine ligand 1 acts in a bidentate fashion to Pd, the amine-bis-phosphinimine ligands 2-5 act in a tridentate fashion, yielding monometallic complexes of varying geometries. In contrast, initial reaction of the amine-bis-phosphinimine ligands with base followed by treatment with NiCl(2)(DME), afforded the amide-bridged bimetallic complexes N(1,2-CH(2)CH(2)N=PR(3))(2)Ni(2)Cl(3) (R = Ph 16, iPr 17) and N(1,2-C(6)H(4)N=PPh(3))(2)Ni(2)Cl(3)18. The precise nature of a number of these complexes were crystallographically characterized.